JP4035553B2 - Method for producing useful composition - Google Patents

Description

The present invention is, from fish waste, to a method for producing a composition comprising a useful compound such as chondroitin sulfate.

  In seafood, many parts that are not generally edible, such as the head, outer skin, and ovarian membrane, are discarded, and the amount of seafood waste is large. On the other hand, useful parts such as chondroitin sulfate, taurine, collagen and the like are also contained in the portion that is not generally edible, and it has been studied to use the useful substances as health foods or raw materials for pharmaceuticals. Accordingly, various methods for producing the useful product from the fishery product waste have been proposed.

  For example, a protein extract obtained by boiling water in salmon nasal cartilage is treated with a proteolytic enzyme, and an adsorbent is added to the resulting solution to degrease, decolorize and deodorize the adsorbent. A method for obtaining a mucopolysaccharide containing chondroitin sulfate by filtering the proteolysate solution containing the material with a filter press, concentrating the filtrate, and drying by spray drying is known (see, for example, Patent Document 1). .

  In addition, the extract obtained by adding water to boiled octopus waste liquid, tuna blood meat, tuna gonad, etc. and boiled is treated with proteolytic enzyme, and adsorbent is added to the resulting solution. A method is known in which after degrading proteins and fine particles are precipitated, the supernatant is concentrated using a reverse osmosis membrane or the like, and taurine is precipitated from the concentrated solution (see, for example, Patent Document 2).

  Also, collagen is extracted into water by adding water to the fish skin or fish bone and heating, and the collagen-containing extract is treated with a protein hydrolase to peptideize the collagen, and the solution contains peptide-modified collagen A method is known in which collagen is obtained by decolorizing and deodorizing by adding activated carbon to the mixture and then concentrating and purifying the filtrate obtained by filtration with a reverse osmosis membrane (see, for example, Patent Document 3).

  As described above, conventionally, when producing useful products from seafood waste such as salmon nasal cartilage, steamed octopus waste liquid, tuna blood meat, tuna gonad, fish skin, fish bones, Protein is extracted from the waste, and the extracted protein is decomposed by treating it with a proteolytic enzyme. Next, an adsorbent such as activated carbon is added to the solution containing the protein degradation product decomposed as described above to degrease, decolorize, and deodorize, and then filtrate to obtain a filtrate. In general, a filter press is used for the filtration. And the target useful substance can be obtained by filtering the said filtrate with a reverse osmosis membrane etc., desalinating, and concentrating.

However, in the conventional technique, an adsorbent such as activated carbon is added to a solution containing a protein degradation product, and after degreasing, decoloring, and deodorizing, the adsorbent such as activated carbon is filtrated by filtration with a filter press. There is an inconvenience of being mixed in. Further, in the conventional technique, in order to obtain the intended useful product, it is necessary to further filter the filtrate obtained by the filter press through a reverse osmosis membrane or the like to perform desalting, concentration or purification. In addition, there are inconveniences that the setting of various conditions relating to filtration largely depends on experience, and the product quality is not stable.
JP 2003-299497 A JP-A-8-20572 JP 2003-238597 A

The present invention is provided to solve such an inconvenience, the fish waste, easily composition comprising a useful compound such as chondroitin sulfate, moreover a method for producing a useful composition which can be obtained in stable quality The purpose is to do.

In order to achieve such an object, a method for producing a useful composition of the present invention comprises an extraction treatment step of extracting a protein into water by treating salmon nasal cartilage in warm water, An enzyme treatment step of adding a proteolytic enzyme to the protein extract to obtain a proteolytic product solution containing the degraded protein, and an enzyme deactivation that heats the proteolytic product solution to deactivate the proteolytic enzyme In addition to the treatment step, an adsorbent is added to the proteolytic product solution in which the proteolytic enzyme has been deactivated to degrease, decolorize, and deodorize, and the proteolytic product solution containing the adsorbent is added to the α- purity alumina 99.56% or more state, and are α- alumina purity of 99.95% or more on the surface, filtered through a microfiltration ceramic filter comprising a diatomite layer on the surface And a filtration treatment step for obtaining an aqueous solution containing chondroitin sulfate as a filtrate.

In the method for producing a useful composition of the present invention, an adsorbent such as activated carbon is added to the protein degradation product solution obtained through the extraction treatment step, the enzyme treatment step, and the enzyme deactivation treatment step to degrease, decolorize, and deodorize. And the protein degradation product solution containing the adsorbent is filtered through the ceramic filter for microfiltration .

The ceramic filter for fine filtration is made of ceramics such as α-alumina, zirconia, titania, and the like, and is used properly according to applications. In the present invention, for example, a ceramic filter for microfiltration comprising α-alumina and having pores having a size in the range of 0.1 to 5 μm can be used. A ceramic filter for microfiltration having pores with a size in the above range has a filtration accuracy in the range of 0.1 to 12 μm.

In the method for producing a useful composition of the present invention, the adsorbent is obtained by filtering the protein degradation product solution containing the adsorbent through the ceramic filter for microfiltration to obtain an aqueous solution containing the useful composition as a filtrate. It is possible to prevent mixing in the filtrate, and at the same time, desalting, concentrating or purifying the intended useful composition can be performed, so that it is not necessary to use a reverse osmosis membrane.

  According to the method for producing a useful composition of the present invention, since the reverse osmosis membrane is not used, various conditions relating to filtration can be theoretically set without depending on experience, and a useful composition having a stable quality. Can be obtained.

  Next, embodiments of the present invention will be described in more detail.

In the method for producing a useful composition of this embodiment, first, a fish-derived waste product is treated in warm water to extract protein in water to obtain a protein extract. As the waste, in the present invention can be used Hana軟bone salmon. The treatment can be performed by adding water to the waste and heating it.

  Next, a proteolytic enzyme is added to the protein extract to obtain a proteolysate solution containing the degraded protein. Examples of the proteolytic enzyme include alkaline protease (for example, Yakult Pharmaceutical Co., Ltd., trade name: Aroase), neutral protease (for example, Yakult Pharmaceutical Co., Ltd., trade name: punchase), pancreatin, papain Etc. The proteolysate thus obtained is, for example, collagen, peptides, amino acids, amino acid derivatives, saccharides bound to proteins, and the like. The protein degradation product solution may contain undegraded protein.

  Next, the proteolytic product solution is heated to inactivate the proteolytic enzyme. The inactivation of the proteolytic enzyme can be performed by heating the proteolytic product solution at a temperature of 90 ° C. for about 5 to 15 minutes, for example.

  Next, an adsorbent is added to the proteolytic product solution in which the proteolytic enzyme has been deactivated, and degreasing, decoloring, and deodorizing are performed. As the adsorbent, activated carbon, diatomaceous earth, or the like can be used.

  Next, the protein degradation product solution containing the adsorbent is filtered through a ceramic filter. As the ceramic filter, for example, a microfiltration ceramic filter made of α-alumina and having pores having a size in the range of 0.1 to 5 μm can be used. A ceramic filter for microfiltration having pores in the above-mentioned range has a filtration accuracy in the range of 0.1 to 12 μm.

  Further, the ceramic filter for microfiltration may be one having a permeability gradient along the flow direction of the protein degradation product solution and a constant permeation flux, and a uniform permeation along the flow direction of the protein degradation solution. It may be provided with sex.

The ceramic filter for microfiltration has α-alumina purity of 99.56% or more in the filter itself, α-alumina purity of 99.95% or more on the surface, Rockwell hardness 85, pressure resistance 10 MPa or more, heat resistance When the pore diameter is 0.2 μm, it has a water permeability of 2000 liters per hour for 1 m ² . The water permeability is 10 times that of a conventional ultrafiltration membrane having the same pore size.

  The ceramic filter for fine filtration is also excellent in chemical resistance and can withstand a 4% -NaOH aqueous solution at 60 ° C and a 2% -NaOH aqueous solution at 90 ° C. Furthermore, the ceramic filter for microfiltration can be washed with a high concentration of acid or alkali at a high temperature and has a lifetime of 10 years or more.

  In the present embodiment, by using the ceramic filter for microfiltration, an operation of filtering the adsorbent from the proteolysate solution to which the adsorbent has been added, and desalting, concentrating or purifying the proteolysate solution The operation can be performed in one behavior at the same time. As a result, an aqueous solution containing a useful composition as a filtrate can be obtained.

  In the present embodiment, various useful compositions can be obtained from various wastes by selecting the ceramic filter for microfiltration according to the purpose. For example, when the waste is salmon nasal cartilage, a composition containing chondroitin sulfate can be obtained as the useful composition by using the ceramic filter for microfiltration. The chondroitin sulfate is a mucopolysaccharide bound to a protein.

  In addition, when the waste is a salmon feature, a composition containing taurine, which is a kind of amino acid, can be obtained as the useful composition by using the ceramic filter for microfiltration.

  When the waste is salmon skin or ovarian membrane, a composition containing collagen can be obtained as the useful composition by using the ceramic filter for microfiltration.

  The ceramic filter for microfiltration can obtain the useful composition having a molecular weight distribution in a desired range by selecting a pore size range. Therefore, the useful composition, for example, the composition containing chondroitin sulfate can be obtained as a health food, or can be used as a raw material for pharmaceuticals.

  According to the production method of the present embodiment, as described above, aqueous solutions of various useful compositions can be obtained from various wastes of seafood, and the useful composition can be obtained by drying the aqueous solution. .

  Next, examples of the present invention will be described.

  In this embodiment, first, 50 liters of water is added to 50 kg of salmon nasal cartilage (hizu (ice-head) chip) and heated until it reaches a temperature of 50 ° C. for a time in the range of 10 to 60 minutes. Protein was extracted into water to obtain a protein extract.

  Next, 100 g of proteolytic enzyme (manufactured by Yakult Pharmaceutical Co., Ltd., trade name: Alloase) was added to the protein extract. The amount of the proteolytic enzyme added is 0.2% by weight with respect to the chip. Then, the protein extract to which the proteolytic enzyme was added was heated for 2 hours at a temperature of 50 ° C. while stirring to obtain a protein degradation product solution. The protein degradation product solution contains a compound in which chondroitin sulfate molecules are crosslinked with calcium.

  Next, the proteolysate solution was heated at 90 ° C. for 5 minutes to inactivate the proteolytic enzyme, and then simply filtered through a 200-mesh filter, and the residual solid was removed by filtration.

  Next, 500 g of activated carbon is added to the filtrate obtained by the simple filtration and heated at a temperature of 60 ° C. for 30 minutes to degrease, decolorize and deodorize the filtrate. Then, hydrochloric acid is added and the filtrate is added. The pH was adjusted to 2. By setting the filtrate to pH 2, the cross-linking of chondroitin sulfate molecules by calcium can be decomposed.

  Next, the filtrate adjusted to pH 2 is filtered through a ceramic filter for microfiltration (trade name: Membralox (registered trademark) ceramic membrane, manufactured by Pall) having uniform permeability along the flow direction of the protein degradation product solution. An aqueous solution containing chondroitin sulfate was obtained. The ceramic filter for microfiltration is made of α-alumina having a purity of 99.56% or more and 99.95% or more on the surface, and has pores having an average diameter of 100 nm.

  The aqueous solution was free of the activated carbon and contained 38.7% by weight of chondroitin sulfate as sodium chondroitin sulfate by the barium sulfate method. The chondroitin sulfate can be obtained by drying the aqueous solution by a method such as spray drying.

  In this embodiment, the filtrate obtained by the simple filtration is degreased, decolored, and deodorized, and then the filtrate is adjusted to pH 2. However, the pH need not be adjusted. When the pH is not adjusted, the filtrate is a fine filter ceramic filter (trade name: manufactured by Paul Co., Ltd.) having a gradient in permeability and a constant flux along the flow direction of the proteolysate solution. (Menbralox GP membrane).

  The ceramic filter for microfiltration that has a gradient in permeability and a constant flux along the flow direction of the proteolysate solution has an α of purity of 99.56% or more and a purity of 99.95% or more on the surface. -It is made of alumina and has a diatomaceous earth layer on the surface. The α-alumina has pores with a diameter of 0.8 μm. According to the ceramic filter for microfiltration having such a configuration, unnecessary substances are unlikely to accumulate on the surface of the filter, and high molecular weight components can also pass therethrough, so that the chondroitin sulfate molecules are permeated while being crosslinked by calcium. An aqueous solution containing chondroitin sulfate can be obtained in a yield equivalent to that obtained when the filtrate is adjusted to pH 2.

  In this example, first, 100 kg of water was added to 100 kg of frozen salmon eyeballs, stirred, thawed and washed.

  After thawing and washing, 100 kg of dehydrated salmon eggs are heated with 300 kg of water until reaching a temperature of 50 ° C. for a time ranging from 10 to 60 minutes, and the protein contained in the salmon eggs is extracted into water to extract the protein. A liquid was obtained. Next, 500 g of the same proteolytic enzyme as used in Example 1 was added to the protein extract, and the mixture was heated at 50 ° C. for 3 hours while stirring.

  Next, the protein degradation product solution is heated at a temperature of 90 ° C. for 15 minutes to deactivate the proteolytic enzyme, and then the upper black component is removed, and the lower layer clear solution is used as the protein degradation product solution. Collected.

  Next, 6 kg of activated carbon was added to the protein degradation product solution and heated at a temperature of 50 ° C. for 20 minutes to degrease, decolorize and deodorize the filtrate.

  Next, the protein degradation product solution is filtered with a ceramic filter for microfiltration (trade name: Membralox (registered trademark) ceramic membrane, manufactured by Pall) having uniform permeability along the flow direction of the protein degradation product solution. An aqueous solution containing taurine was obtained. The ceramic filter for microfiltration is made of α-alumina having a purity of 99.56% or more and 99.95% or more on the surface, and has pores with a diameter of 100 nm.

  The aqueous solution was free of the activated carbon and contained 87 mg / 100 g of taurine and 30% by weight of collagen. The taurine can be obtained by drying the aqueous solution by a method such as spray drying.

  In this example, first, 160 liters of water is added to 80 kg of salmon ovary membrane and heated until reaching a temperature of 50 ° C. for a time ranging from 10 to 60 minutes, and the protein contained in the salmon ovary membrane is extracted into water. To obtain a protein extract.

  Next, 800 g of the same proteolytic enzyme as used in Example 1 was added to the protein extract and heated at a temperature of 50 ° C. for 4 hours with stirring to obtain a proteolysate solution.

  Next, the proteolysate solution was heated at 90 ° C. for 5 minutes to inactivate the proteolytic enzyme, and then simply filtered through a 200-mesh filter, and the residual solid was removed by filtration.

  Next, 800 g of activated carbon was added to the filtrate obtained by the simple filtration, and the filtrate was degreased, decolored, and deodorized by heating at 60 ° C. for 30 minutes.

  Next, the protein degradation product solution is filtered with a ceramic filter for microfiltration (trade name: Membralox (registered trademark) ceramic membrane, manufactured by Pall) having uniform permeability along the flow direction of the protein degradation product solution. An aqueous solution containing collagen was obtained. The ceramic filter for microfiltration is made of α-alumina having a purity of 99.56% or more and 99.95% or more on the surface, and has pores with a diameter of 100 nm.

  The aqueous solution was not mixed with the activated carbon and contained 10% by weight of collagen. The collagen can be obtained by drying the aqueous solution by a method such as spray drying.

  In this example, salmon ovary membrane is described. However, when salmon skin is used instead of salmon ovary membrane, collagen can be obtained by processing in the same manner as in this example. it can. Examples of the skin of the salmon include the skin of the salmon head.

Claims (1)

An extraction process for extracting protein into water by treating salmon nasal cartilage in warm water; and
An enzyme treatment step of adding a proteolytic enzyme to the protein extract to obtain a proteolytic product solution containing the degraded protein;
Heating the proteolysate solution to inactivate the proteolytic enzyme;
An adsorbent is added to the proteolysate solution in which the proteolytic enzyme has been deactivated to degrease, decolorize, and deodorize, and the proteolyte solution containing the adsorbent is purified from α-alumina purity of the filter itself 99.56% or more state, and are α- alumina purity of 99.95% or more in the surface, is filtered by microfiltration ceramic filter comprising a diatomite layer on the surface, filtration to obtain an aqueous solution containing chondroitin sulfate as the filtrate And a process for producing a useful composition.